Process for the preparation of polymeric amine containing products

ABSTRACT

A process of forming polymeric products having a high degree of pendant secondary or tertiary alkylene amino groups by contacting, in a liquid media, a hydrocarbon polymer having olefinic groups therein with a primary or secondary amine, carbon monoxide and hydrogen in the presence of a catalytic amount of a Group VIII metal compound.

BACKGROUND OF THE INVENTION

The present invention relates to the preparation of amino substitutedpolymeric hydrocarbons and, more particularly, to a process for formingpolymeric products having a hydrocarbon backbone and a large amount ofpendant secondary and/or tertiary alkyleneamine groups by the reactionof polymeric hydrocarbons having olefinic groups therein with hydrogen,carbon monoxide, and a primary and/or secondary amine in the presence ofa catalytic amount of a Group VIII metal compound.

Catalytic aminomethylation of monoolefins with monomeric secondarymonoamines, carbon monoxide and hydrogen is well known and was initiallytaught by Dr. Walter Reppe in Experimentia, Vol. 5, p. 93 (1949); GermanPat. No. 839,800 (1952) and Liebigs Ann. Chem., Vol. 582, p. 148 (1953).The process was, however, of limited value due to the required use oflarge quantities of toxic iron or nickel carbonyls as the catalyst, therapid rate of consumption of the catalyst, the slow rate of reaction,poor selectivity and the poor yields of product. Moreover, the reactionwas taught to be restricted to monoolefins and to low molecular weightmonoamines.

Aminomethylation of other monoolefins has been carried out in thepresence of other metal carbonyls, but the reactions have been found tobe non-selective and produce, at best, only moderate yields of amines.For example, U.S. Pat. Nos. 2,422,631 and 3,234,283 disclose that lowerolefins, carbon monoxide, hydrogen, and a secondary monoamine will form,in low yields, tertiary amines in the presence of cobalt hydrocarbonylor dicobalt octocarbonyl as well as certain other cobalt compounds.

More recently, U.S. Pat. Nos. 3,513,200 and 4,096,150 have disclosed theutilization of Group VIII metal compounds as suitable compounds tocatalyze the reaction between monoamines and monoolefins with hydrogenand carbon monoxide to form low molecular weight monomeric tertiaryamines. These reactions, however, generally only provide the desiredproduct in low yields while forming significant amounts of by-products.

In addition, U.S. Pat. No. 4,312,965 may be referred to as teaching theformation of a polymeric product having a mixture of amine and amidependant groups by contacting a polymer with an amine, carbon monoxideand water in the presence of a rhodium metal compound. The required useof water as the hydrogen source and rhodium as the catalytic metal istaught to provide a means of aminomethylation of the polymericpolyolefin. The process, however, yields a product having low degrees ofamine incorporation and, therefore, does not provide for a highly activepolymer normally desired for commercial utilization. The above and otherreferences teach that aminomethylation generally leads to the formationof significant quantities of undesired by-products. This is confirmed ingeneral treatises such as: "Carbon monoxide in Organic Synthesis" ofFalbe.

In general, the yields of desired amine incorporation in previouslyformed polymeric material and of monomeric amine products byaminomethylation has been viewed by those skilled in this art as beingpoor at best.

SUMMARY OF THE INVENTION

The present invention is directed to a one-step, cost efficient methodof forming polymeric products having a hydrocarbon backbone and a highdegree of alkylene alkylamine pendant groups by contacting, in a liquidmedia, a polymer having unsaturated groups therein, a primary orsecondary amine, carbon monoxide and hydrogen gas in presence of a GroupVIII organometallic compound. The formed product is useful for a varietyof applications, e.g. as a surfactant, a flocculating agent, softener,and as a component in coating compositions.

DETAILED DESCRIPTION OF THE INVENTION

The subject invention is directed to a new one-step, cost efficientcatalytic method of forming polymeric polyamines having a structure of ahydrocarbon backbone and pendant amino groups which are connected to thepolymer backbone by an alkylene bridge. The method is achieved bycontacting, in an inert solvent, a polymer having a multiplicity ofolefinic unsaturation therein, hydrogen, carbon monoxide and a primaryor secondary amine in the presence of a Group VIII metal compound asmore completely described hereinbelow.

The aminomethylation of the olefinic containing polymer has beenunexpectedly found to produce a polymer product having a high degree ofincorporation of alkylene alkylamine pendant groups when formedaccording to the presently described method requiring the utilization ofhydrogen and the presence of at least one Group VIII organometalliccompound as described hereinbelow. Although aminomethylation ofpolymeric materials has been previously described, in U.S. Pat. No.4,312,965, as being capable of providing products having amine/amidependant groups if one uses the required water and a rhodium metalcompound as the catalyst, the process has several defects. The primarydefect is one which is common to aminomethylation reactions (even whensimple, small olefinic compounds and/or other catalyst materials areused), and that is the low degree of formation of amino containingcompounds or low degree of incorporation of amino groups onto thepolymer product by the process described in U.S. Pat. No. 4,312,965. Incontrast, it has been presently unexpectedly found that by performingthe aminomethylation using the conditions described herein,specifically, using a single organic liquid phase, hydrogen as thehydrogen source and Group VIII organometallic compounds as the catalyst,one unexpectedly achieves a polymeric product having a combination ofdesired properties. The polymeric product presently attained has (a) ahigher degree of alkylene alkylamine pendant groups therein thanpossible by prior known methods, (b) substantially no residual amount ofolefinic groups in the backbone of the polymer, (c) substantially noamido groups (a generally undesired group due to its inactivity orsubstantially low activity with respect to polyamine utilities), (d)absence of Schiff's base, aldehyde and enamine groups normally found insmall amounts in prior art aminomethylation products and (e) increasedstability of the polymeric polyamine product and reduced tendency to gelin comparison to products formed by prior art methods.

The present process has also been unexpectedly found very effective informing polymeric polyamines with high concentration of alkylene aminegroups from high molecular weight olefinic containing polymers. Suchability provides a method to produce unique amine polymers of highmolecular weight. Finally, the instant process, due to its highefficiency in incorporating amines into the polymeric reactant, has beenfound useful in forming unique amine containing polymers havingsubstantial amine groups therein even when the olefinic concentration islow in the polymer reactant (e.g. EPDM polymers).

The olefinic containing polymers useful herein can be formed frommonomers having multiple olefinic groups therein alone (homopolymers),or in combination with other monomers, by conventional cationic,anionic, free radical, coordination or supported metal catalyticprocesses, as are well known by the artisan. The term "olefiniccontaining polymer" or "olefinic prepolymer", as used herein, is meantto define homopolymers and copolymers which contain a multiplicity ofolefinic bonds distributed throughout the polymer chain either as a partof the polymer backbone or as a part of the pendant group. The averagemolecular weight of the olefinic containing polymer should be at leastabout 500 and preferably from about 500 to 200,000 and above. Thesubject process has been found to be an especially effective method whenprocessing high molecular weight olefinic containing polymers having anaverage molecular weight of from about 10,000 to 200,000 to readilyprovide a high molecular weight polymeric polyamine. Incorporation ofamino groups in high molecular weight polymer starting materials isdifficult, at best, by previously known techniques.

The olefinic containing polymers useful herein can be homopolymersformed from C₄ to C₁₀ monomers having multiple olefinic groups therein,such as, for example, from butadiene; isoprene, cyclopentadiene; dimersof cyclopentadiene; 1,3-pentadiene; 1,4-pentadiene; 1,3-hexadiene;1,4-hexadiene; 1,5-hexadiene; 2,4-hexadiene; 1,3,5-hexatriene and thelike, as well as such monomers containing substituents thereon which areinert with respect to aminomethylation, such as C₁ -C₃ alkyl, halo andcarbonyl radicals. The olefinic containing polymer used in the subjectinvention may be in any of their isomeric stereoconfigurations. In thecase of polybutadiene, for example, it can be in its cis-1,4-;trans-1,4-; or trans-1,2 configuration or a mixture thereof. Further,the polymers useful herein may be copolymers formed from two or moremonomer compounds which are each capable of forming a polymeric segmentcontaining olefin bonds therein, such as copolymers having polybutadienesegments as, for example, copolymers of poly(butadiene-isoprene),poly(butadiene-1,4-pentadiene) and the like.

The olefinic containing polymers useful herein can also be copolymersformed from at least one monomer as described above capable of producingolefin containing polymer segments and at least one copolymerizablevinyl monomer which does not form olefin containing polymer segments,such as acrylamides, acrylonitrile, styrene, actylates, alkyl vinylethers, alkyl vinyl ketone and the like, and mixtures thereof, and C₁-C₂₀ hydrocarbyl derivates of such monomers, such as alpha-methylstyrene, methyl methacrylate and the like. Such materials are formed inconventional manners by free radical, cationic or anionic polymerizationtechniques, as are well known. A large variety of these polymers can bereadily obtained commercially, such as poly(butadiene-acrylonitrile),poly(butadiene-styrene), acrylonitrile-butadiene-styrene (ABS) resins,ethylene-propylene-diene (EPDM) polymers or the like. The olefiniccontaining polymers can be formed with non-olefin containing monomergroups in any degree desired as long as the resultant polymer containssufficient amounts of olefinic bonds therein to act as an activeprecursor of the desired amine containing polymer product. It isdesirable that the copolymers contain at least about 3 percent by weightof olefinic containing polymer segments therein and, preferably, thatthe copolymer contain at least about 30 percent by weight of theolefinic containing polymer segments.

The polymers found useful as reactants in accordance with the presentprocess can also be formed from olefinic monomers such as propylene,butylene, cyclopentene decylene and the like which produce, throughbranching, isomerization and the like polymeric material having residualolefinic bonds therein. In addition, asphalts and asphaltenecompositions can also be used herein. The particular olefinic containingpolymer to be used will, of course, depend on the nature of theresultant polyamine polymers desired.

The primary or secondary amine group containing reactant can be selectedfrom compounds having the formula: ##STR1## wherein R is selected fromhydrogen or a C₁ -C₂₀ hydrocarbon radical, such as alkyl, aryl, alkaryl,aralkyl, and cycloalkyl groups, preferably a C₁ -C₆ alkyl, aryl orcycloalkyl groups and R¹ is selected from a C₁ -C₂₀, preferably a C₁ -C₆hydrocarbon radical as described with respect to R above. Illustrativeexamples of amines found suitable as a reactant in the present processare methylamine, ethylamine, propylamine, butylamine, n-pentylamine,hexylamine, decylamine, dodecylamine, dimethylamine, diethylamine,dipropylamine, diisopropyl amine, di-n-butylamine, diisobutylamine,dipentylamine, di-2,2,4-trimethylpentylamine, dihexylamineethylhexylamine diheptylamine, dinonylamine, butylpentadecylamine,diphenylamine, ditolylamine, methylcumenylamine, dibenzylamine, anilinemethyl-2-phenylethylamine, methylnapthylamine, diidenylamine,di-m-xylylamine, dioctenylamine, dipentenylamine, methylbutenylamine,dicyclopentylamine, di(methylcyclopentyl)amine, and butylcylococtylamineand the like. In addition, R and R¹ can be joined to form a singlealkylene radical having from 2 to 6 carbon atoms, as illustrated bypyrrolidine and the like. Each R and R' or the joined R-R' alkyleneradical can contain hetero atoms or groups which are substantiallynon-reactive with respect to the aminomethylation reaction as presentlydescribed. Such heteroatoms can be oxygen, sulfur or tertiary orhindered secondary nitrogen and the like and such groups can be ethersalcohols, thioalcohols, thioethers, amido, cyano, tertiary amino andsterically hindered secondary amino groups. Illustrative examples ofamine reactants containing such heteroatom or group are morpholine,aminoethanol, 4-amino-2,2,6,6-tetraalkyl piperidine and the like.

The reaction is performed under a liquid phase formed by an organicliquid which is a solvent for the polymer reactant and the amine. It ispreferred that an anhydrous liquid phase be used. The presence of small(less than 5 percent of total liquid) amount of water may be toleratedbut is not preferred as its presence tends to inhibit achieving thedesired high degree of amine incorporation. Any suitable organichydrocarbon liquid can be employed which is inert to the reactionconditions, the reactants, the catalyst and the products. Examples ofsuitable hydrocarbons include aromatic hydrocarbons such as benzene,toluene, xylene, ethyl benzene, tetraline, etc., aliphatic hydrocarbonssuch as butane, pentane, isopentane, hexane, isohexane, heptane, octane,isooctane, nephtha, gasoline, kerosene, mineral oil, etc., alicyclichydrocarbons, such as cyclopentane, cyclohexane, methylcyclopentane,decalin, indane, etc.

Ethers can also be employed as the reaction solvent, such as diisopropylether, di-n-butyl ether, ethylene glycol diisobutyl ether, methylo-tolyl ether, ethylene glycol dibutyl ether, diisoamyl ether, methylp-tolyl ether, methyl m-tolyl ether, ethylene glycol diisoamyl ether,diethylene glycol diethyl ether, ethylbenzyl ether, diethylene glycoldiethyl ether, diethylene glycol dimethyl ether, ethylene glycol diethylether, ethylene glycol diphenyl ether, triethylene glycol diethyl ether,diethylene glycol di-n-hexyl ether, tetraethylene glycol dimethyl ether,tetraethylene glycol dibutyl ether, dioxane, tetrahydrofuran etc.

Alcohols can also be employed as a reaction solvent. The alcohols can beany primary, secondary or tertiary alcohol which are liquid at bothambient and reaction conditions. It is preferred that the alcohol be aC₁ -C₈ alcohol such as, for example methanol, ethanol, isopropanol,n-butanol, iso-butanol, t-butanol, t-amyl alcohol, 2-pentanol,3-ethyl-2-pentanol and the like.

Tertiary amines can also be employed as the reaction solvent, thenitrogen atom, by definition, being substituted with three hydrocarbylgroups which are inert with respect to the reaction, such as, forexample, alkyl, aryl, alkaryl, aralkyl groups and the like. Examples ofsuitable tertiary amines include triethylamine, tripropylamine,triisobutylamine, trihexylamine, triheptylamine, triamylamine, dibenzylethylamine, dibutyl ethylamine, dimethyl pentylamine, diphenylethylamine, diphenyl methylamine, dimethyl aniline, pyridine, dimethylpyridine, methoxy pyridine, methyl pyrrolidine, ethyl pyrrolidine andthe like.

The particular solvent to be used will depend on its ability to remainin the liquid state at both ambient and at reaction conditions tofacilitate the mixing of the components, its solvating ability withrespect to the polymer and amine reactants, and its ease of handling, ascan be readily determined by the artisan.

The reaction is performed under relatively mild conditions includingtemperatures from about 100° to about 250° C.; preferably from about125° to about 200° C. Sufficient pressure should be used to maintain thereaction medium in a liquid phase. The reaction should be carried out ata pressure of from about 30 to about 300 atmospheres and, preferably,from about 30 to 150 atmospheres. The pressure can be maintained by thepressure of the carbon monoxide and hydrogen supplied to the reactionzone. If desired, a suitable inert gas, such as nitrogen, can also becharged to the reaction zone to increase the pressure within thereaction zone.

The ratio of the reactants can be widely varied. The mole ratio ofhydrogen to olefinic double bonds should be at least about 2:1 with fromabout 2:1 to 20:1 being preferred. The molar ratio of carbon monoxide toolefinic double bond should be at least 1:1. The carbon monoxide can beused in excess to form sufficient pressure required in the reactionzone, as described above. Finally, the mole ratio of amine reactant toolefinic double bond contained in the polymer should be at least about1:1 or greater and preferably from at least about 1.2:1 or greater withfrom about 1.2:1 to 20:1 being most preferred.

The catalyst required to be used in the present method to achieve thehigh degree of amine incorporated polymer product comprises at least onecompound having a Group VIII metal of the Periodic Chart therein (theterm "Group VIII metal compound" or "catalyst" as used herein is meantto describe such compounds). Such Group VIII metal compounds can beinorganic compounds, such as, for example, Group VIII metal salts,oxides, carbonyls and the like. The Group VIII metal compound can be anorganometallic such as, for example, (although rhodium metalorganometallic compounds are given here for illustrative purposes it isunderstood that other similar Group VIII metal compounds can be used)tetrarhodium dodecacarbonyl, hexarhodium hexadecacarbonyl,tris(dimethylphenylphosphine) norbornadiene rhdodiumhexafluorophosphate, bis(1,2 diphenylphosphino) ethane norbornadienerhodium perchlorate, chlorobis(ethylene) rhodium dimer,chloro(1,5-cyclooctadiene) rhodium dimer, chlorodicarbonylrhodium dimer,chloropentaaminerhodium chloride, hydridocarbonyltris(triphenylphosphine) rhodium, rhodium acetate dimer, rhodiumacetylacetonate, sodium hexachlororhodate hydrate,dicarbonylacetylacetonato rhodium, chlorocarbonylbis(triphenylphosphine)rhodium, chlorochiorbonyl p-toluidine rhodium and trichloro rhodiumpyridine. The preferred catalyst to be used by the present process areformed from Group VIII metal compounds of the metals, rhodium, rutheniumand iridium and most preferably those formed from a mixture of at leasttwo compounds of Group VIII metals selected from rhodium, ruthenium oriridium. When mixtures of compounds are used it is preferred that arhodium containing compound be present and be the minor component of themixture. The most preferred catalyst used in the present process aremixtures of a rhodium compound and a ruthenium compound. Of suchmixtures the best catalytic activity is attained when the ratio ofrhodium metal atom to ruthenium metal atom is less than about 0.5.

The exact chemical and physical composition of the entity which acts asthe catalyst for the subject reaction is not known with certaintybecause of the possible restructuring and/or interaction of the metalcompound and the reactants contained in the reaction zone. Whether theGroup VIII compounds described herein acts directly as the catalyst oras the precursor for the catalyst entity which causes the presentlydesired aminomethylation is immaterial. The subject Group VIII metalcompounds will be referred herein as the "catalyst" as they haveunexpectedly been found, when used with hydrogen, to directly and/orindirectly provide the desired polymers having high amine incorporationby the present one-step process and to give the desired product in goodyields.

The catalyst found useful in the subject process can be a Group VIIImetal salt of an inorganic acid such as, for example, a chloride,nitrate, sulfate, perchlorate or the like inorganic salt or of anorganic acid salt such as an acetate or the like. The salts are wellknown commercial products formed conventionally by the reaction of themetal oxide with an acid. The salt can be used in its anhydrous state oras a hydrated salt.

The catalyst of the subject process can be an organometallic compound.Such compounds can be formed in coordination with the metal in any oneof its valence states. The organometallic compounds are normally formedfrom chemical moieties which contain unshared electrons such as atomsselected from nitrogen, oxygen, phosphorous or sulfur or which containsunsaturation. The compounds can be in the form of a carbonyl; an olefinsuch as ethylene, butene and the like; diolefines, such asnorbornodiene, cyclooctadien-1,5 and the like; aliphatic, aromatic, arylaliphatic phosphites, such as triethyl phosphite, tributyl phosphite,trimethyl phosphite, triphenyl phosphite, dimethylphenyl phosphite,tritolyl phosphite, tribenzyl phosphite, ditolyl phenyl phosphite, andthe like; aliphatic, aromatic, aryl aliphatic phosphines such astriphenyl phosphine and the like wherein the phosphine to metal is equalor less than 3; aliphatic and cyclic ethers such as dimethyl and diethyloxide, dioxane, dialkyl ether glycols, acetyl acetone and the like;primary, secondary, and tertiary amines which contain alkyl, aryl,alkaryl, arallayl cycloalkyl groups or mixtures thereof such astrimethyl amine, diethyl amine, toluidine and the like; heterocyclicbases such as pyridine, and the like; ammonia, sulfides such as dialkyl,diaryl, alicyclic heterocyclic sulfides and the like and mixturesthereof. When the compound is formed from uncharged ligand componentswith a charged Group VIII metal, the compound is formed into a stableneutral state with an anion such as a chloride, perchlorate, nitrate,hexaflourophosphate and the like.

The catalyst can be added directly to the reaction liquid phase eitherprior to, with or subsequent to the introduction of other requiredreactants. The Group VIII metal compound which are useful as a catalystin the present process must have some degree of solubility in the liquidmedia in which the subject aminomethylation takes place. The choice ofliquid media and/or catalyst to be used in a particular reaction so thatthe catalyst has some degree of solubility can be readily determined bythe artisan using conventional methods.

The catalyst has been found to be effective to cause the formation ofthe desired polymeric polyamines as described above when used in a molarratio of Group VIII metal atom to olefin bond of from about 1×10⁻⁵ to2.5×10⁻³ and preferably from about 1×10⁻⁵ to 1×10⁻³. The most preferredrange from both effectiveness and economy is from 5×10⁻⁵ to 5×10⁻⁴.Although greater amounts of catalyst can be used, such has not beenfound required.

The process is carried out by contacting the above described reactantsand the catalyst in a vessel which is preferably adapted for gasinjection, agitation and heating. The polyolefin, the amine, and thecatalyst are added to the solvent and the reaction mixture ispressurized and heated. The reactor and its contents are maintained atthe desired elevated temperature and pressure for a sufficient period tocause the formation of the desired polymeric secondary amine. The vesselis then cooled and when appropriate, degassed and the polymeric productis recovered by standard technique such as by precipitation in anon-solvent or extraction and drying in a vacuum. For additionalpurification the product may be further subjected to fractionalprecipitation and the quantity of desired product may be determined bystandard analytical techniques.

The following examples are given for illustrative purposes only and arenot meant to be a limitation on the subject invention as defined in theappended claims. All parts and percentages are by weight unlessotherwise indicated.

The preparations of polymeric polyamines were conducted using, unlessotherwise indicated hereinbelow, 0.75 part (14 mmole C═C) polybutadienewith 22.4 mmoles amine reactant in the presence of a Group VIII metalcatalyst as specifically indicated below. The reactants were dilutedwith tetrahydrofuran to form a 10 ml mixture. The mix was charged into a150 ml Hoke cylinder reactor which was then pressurized with CO and H₂in a 1:1 molar ratio to 1000 psi. The reactor was heated to 150° C. andmaintained there for a period of 4 hours. The polymer product wasrecovered from the reaction mixture by organic solvent/water extraction.

The product was analyzed by standard Nuclear Magnetic Resonance (NMR)using a Varian EM 390. In addition, selective determination of amineincorporation was done by the standard techniques of (a) determining thetotal amine incorporation by direct titration with hydrochloric acid inisopropanol; (b) determining secondary and tertiary amine content byfirst reacting any residual primary amine present with salicyladehydeand then titration with hydrochloric acid in isopropanol for secondaryand tertiary amine content; and (c) treating a sample withphenylisothiocyanate to react primary and secondary amines and thentitrate with hydrochloric acid in isopropanol to determine concentrationof tertiary amino groups in the polymer product. The results from a, b,and c allows one to calculate primary, secondary and tertiary aminogroups, as appropriate, for the reactant and product.

EXAMPLE 1

A series of products were formed from polybutadiene with a variety ofamines, of liquid reaction media, of concentration of catalyst, oftemperature and of polymer molecular weight. The amine to olefinicdouble bond molar ratio was 1.6. The reactants were dissolved intetrahydrofuran or N-methyl pyrrolidine. The reactants were added to a150 ml Hoke cyclinder reactor, pressurized with CO/H₂ in a 1:1 molarratio or with equal amount of CO with inert gas (N₂) where water wasused in lieu of H₂ for comparative purposes. The reactor was heated tothe indicated temperature for a period of 5 hours, cooled and theproduct recovered and analyzed by titration and NMR. For each of thereactions, a duplicate back-to-back comparative reaction was conductedto show the benefit of using the combination of a Group VIII metalcatalyst with hydrogen instead of the combination of the metal andwater.

Further, samples of series 1, 2 and 3 further show that the resultantproduct has a significant reduction in residual unsaturation in thepolymers and thereby forms a more stable material.

The results are listed in Table I below.

                                      TABLE I    __________________________________________________________________________    Comparison of Polyamine Synthesis in    Presence of Hydrogen vs. Water              Polymer.sup.(a)    Hydrogen  MW                 Catalyst.sup.(d)                                          Temp.                                              Product.sup.(e)    Sample        Source              g/mol Amine   Solvent.sup.(c)                                 (4)                                    C = C/Rh                                          °C.                                              % AI                                                  % Unsat.    __________________________________________________________________________    1   H.sub.2              1000  Morpholine                            THF  RhH                                    2000  125 42  15    1   H.sub.2 O              1000  Morpholine                            THF  RhH                                    2000  125 10  60    1(c')        H.sub.2 O              1000  Morpholine                            THF  RhH                                    2000  150  4   8    2   H.sub.2              1000  Morpholine                            THF  Rh.sup.⊕                                    2000  125 30  15    2(c)        H.sub.2 O              1000  Morpholine                            THF  Rh.sup.⊕                                    2000  125 10  67    3   H.sub.2              1000  Morpholine                            NMP  Rh.sup.⊕                                    2000  125 42  25    3(c)        H.sub.2 O              1000  Morpholine                            NMP  Rh.sup.⊕                                    2000  125 10  67    4   H.sub.2              1000  Dimethylamine                            THF  Rh.sub.6                                    2000  150 49    4(c)        H.sub.2 O              1000  Dimethylamine                            THF  Rh.sub.6                                    2000  150  5    5   H.sub.2              2600.sup.(b)                    Dimethylamine                            THF  Rh.sub.6                                    1000  125 64    5(c)        H.sub.2 O              2600  Dimethylamine                            THF  Rh.sub.6                                    1000  125  6    6   H.sub.2              2600  Dimethylamine                            THF  Rh.sub.6                                    1000  150 75    6(c)        H.sub.2 O              2600  Dimethylamine                            THF  Rh.sub.6                                    1000  150  4    __________________________________________________________________________     .sup.(a) Phenyl terminated polybutadiene, 25% vinyl, 99% unsaturation     .sup.(b) 50% vinyl, 25% trans, 99% unsaturation     .sup.(c) THF = tetrahydrofuran; NMP = N--methylpyrrolodine     .sup.(6) RhH = RhH(CO) (Pφ.sub.3).sub.3, Rh.sub.6 = Rh.sub.6     (CO).sub.16, Rh.sup.⊕ = [Rh(NBD) (Ph(CH.sub.3).sub.2).sub.3 ]PF.sub.6     (NBD  norbornadiene)     .sup.(e) AI = Amine incorporation; Unsat. = Unsaturation; % AI determined     by selective titration; % Unsat. determined by 'H--NMR

EXAMPLE 2

0.75 part polybutadiene having a molecular weight of 1000, 1.30 partsisopropylamine, 0.0028 part Rh₆ (CO)₁₆ was dissolved in tetrahydrofuran(15%) and the reaction mixture placed in a 150 ml Hoke cylinder whichwas pressurized to 1,000 psi with carbon monoxide and hydrogen (CO/H₂=1:1). The temperature was raised to 150° C. over 90 minutes andmaintained there for 4.5 hours. The product mixture was analyzed byconventional titration methods, with standardized hydrochloric acid inisopropanol to determine the total amount of amino groups incorporatedin the polymer and by selective titration to determine the ratio ofsecondary and tertiary amino groups. 51% of the double bonds were foundto be aminomethylated. The ratio of secondary to tertiary amine was 4:1.

EXAMPLE 3

This reaction was carried out in the same way as described in Example 2,the difference being that 2.21 parts cyclohexylamine was used asstarting material. 54.6% of the double bonds were found to beaminomethylated.

EXAMPLE 4

This reaction was carried out in the same way as described in Example 2,the difference being that 1.60 parts tert-butylamine was used asstarting material. 48.9% of the carbon double bonds were found to beaminomethylated.

EXAMPLE 5

In each of the following series of samples polybutadiene and aminecompound, as identified in the table below, (amine/C═C=1.6 molar ratio)were dissolved in tetrahydrofuran. Rh₆ (CO)₁₆ was added in amount toprovide one Rh atom per 500 C═C bonds. The reactants were added to a 150ml Hoke cyclinder reactor or a 2 liter Magnadrive autoclave, asindicated, and then pressurized to 1000 psi with CO/H₂ in a 1:1 molarratio. The reactor was heated to 150° C. for about 5 hours, cooled andthe product recovered and analyzed. The results are given in Table IIbelow.

                  TABLE II    ______________________________________    Scope of the Aminomethylation Reaction in Respect to    Different Polybutadienes as starting Materials.sup.(a)                                         Amine In-    Mol. Wt..sup.(a)            % cis +.sup.(e)                      % 1,2(Vinyl).sup.(e)                                  Nitrogen                                         corporation    g/Mol.  trans units                      units       Source.sup.(b)                                         %    ______________________________________     4,500.sup.(c)            55        45          DMA    70     14,000.sup.(c)            20        80          DMA    53     30,000.sup.(c)            20        80          DMA    51    156,000.sup.(c)            100       --          DMA    49     1,000.sup.(d)            10        90          DMA    82     3,000.sup.(d)            10        90          iPrAm  84    ______________________________________     .sup.(a) Molecular weight of the polybutadiene.     .sup.(b) DMA = dimethylamine, iPrAm = isopropylamine     .sup.(c) 150 ml Hoke cylinder used as reactor     .sup.(d) 2 liter Magnadrive (Autoclave Engineering) autoclave used as     reactor.     .sup.(e) double bond distribution of starting butadiene polymer.

EXAMPLE 6

A series of experiments were conducted according to the procedure ofExample 5 above. The polymer used in each experiment was a phenylterminated polybutadiene of MW of 1000 having 25% vinyl double bonds,99% unsaturation. The amine was varied as indicated in Table III below.The amine incorporation was determined by selective titration method.Hydrogen was used in each experiment with Rh₆ (CO)₁₆, as the Group VIIImetal catalyst.

                  TABLE III    ______________________________________                                    Polymer               Catalyst Conc.       Amine    Amine      C = C per Group VIII metal                                    Incorp.    ______________________________________    Pyrrolidine               2000                 64    Dimethylamine               2000                 49    Isopropylamine               1000                 51    Cyclohexylamine               1000                 55    t-butylamine               1000                 49    Methylamine                500                 63    ______________________________________

EXAMPLE 7

A series of products were formed according to the procedure of Example 5above except that the catalyst used was composed of a mixture of GroupVIII metal compounds as indicated in Table IV below. In each casehydrogen was used as the hydrogen source to provide, in combination withthe catalyst, a high incorporation of amino groups into the polymer.Sample 6c is included for comparative purposes to show that much loweramine incorporation is attained when water is used as the hydrogensource.

                                      TABLE IV    __________________________________________________________________________    Aminomethylation with Mixed Metal Systems                                     Polymer                                     Amine                     Catalyst  Hydrogen                                     Incorp.    Sample        Catalyst     Amount.sup.(b)                           Amine                               Source                                     (%)    __________________________________________________________________________         ##STR2##                      ##STR3##                           DMA H.sub.2                                     61     2         ##STR4##                      ##STR5##                           DMA H.sub.2                                     80     3         ##STR6##                      ##STR7##                           DMA H.sub.2                                     74     4         ##STR8##                      ##STR9##                           DMA H.sub.2                                     74     5         ##STR10##                      ##STR11##                           DMA H.sub.2                                     62     6         ##STR12##                      ##STR13##                           DMA H.sub.2                                     71     6.sup.(c)         ##STR14##                      ##STR15##                           DMA H.sub.2 O                                     26    __________________________________________________________________________     .sup.(a) determined by selective titration     .sup.(b) [C = C]/[Metal]     Rh.sup.+ = [Rh(NBD)Ph((CH.sub.3).sub.2).sub.3 ]PF.sub.6 (NBD =     norbornadiene)     DMA = dimethylamine

What is claimed is:
 1. A process of forming polymeric products having ahydrocarbon backbone and secondary or tertiary or mixed alkyleneaminependant groups comprising contacting in a reaction zone, a mixture of aninert substantially anhydrous, organic liquid media, a polymerichydrocarbon having olefinic groups present in its hydrocarbon backbone,a primary or secondary amine, carbon monoxide and hydrogen heating saidmixture at a temperature of from about 100° C. to about 250° C. at apressure of from about 30 to 300 atmospheres in the presence of acatalytic amount of at least one Group VIII metal containing compoundfor a sufficient period of time to cause the formation of the polymericpolyamine product, and recovering said polymeric polyamine product. 2.The process of claim 1 wherein the Group VIII metal containing compoundis a mixture of compounds having at least two different Group VIIImetals therein.
 3. The process of claim 2 wherein at least one compoundof said mixture is a rhodium compound.
 4. The process of claim 2 whereinsaid mixture is selected from mixtures comprising a mixture of at leastone rhodium compound with at least one ruthenium compound or a mixtureof at least one rhodium compound and at least one iridium compound. 5.The process of claim 2 wherein the Group VIII metal containing compoundis a mixture of at least two compounds, such that at least one compoundis a rhodium containing compound and at least one compound is aruthenium containing compound the ratio of rhodium to ruthenium is lessthan about 0.5.
 6. The process of claim 2 wherein the polymerichydrocarbon is selected from polybutadiene or polyisoprene.
 7. Theprocess of claim 2 wherein the amine reactant has the general formula:##STR16## wherein R is selected from hydrogen or a C₁ -C₂₀ hydrocarbonradical, R' is selected from a C₁ -C₂₀ hydrocarbon radical or R and R'are, in combination, a C₂ -C₆ alkylene radical.
 8. The process of claim2 wherein the amine reactant is a C₁ -C₆ primary or secondary amineselected from alkyl amines, heteroalkylamines cycloalkylamines andheterocycloalkylamines wherein the heteroatom is nitrogen, oxygen orsulfur.
 9. The process of claim 2 wherein the amine reactant is anarylamine.
 10. The process of claim 2 wherein the amine reactant is acompound in which each R and R' group is independently selected from aC₁ -C₆ hydrocarbon radical.
 11. The process of claim 2 wherein the molarratio of carbon monoxide to olefinic double bond is at least about 1:1;of hydrogen gas to olefinic double bond is at least about 2:1; and ofamine to olefinic double bond is at least 1:1.
 12. The process of claim11 wherein the molar ratio of CO to double bond is 1:1 to 20:1; ofhydrogen to double bond is 2:1 to 20:1 and of amine to double bond is1.2:1 to 20:1.
 13. The process of claim 2 wherein the reactiontemperature is from about 125° to 200° C. and the pressure is from about30 to 150 atmospheres.
 14. The process of claim 2 wherein the inertliquid contains up to 5 percent water therein.
 15. The process of claim2 wherein the inert liquid is anhydrous.